Photocrosslinkable carbonyl-containing polymeric composition and element with cobalt complex

Abstract

There is disclosed a composition, element, and process of imaging, wherein a polymeric binder is rendered photocrosslinkable by virtue of a photoresponsive source of amines, and by virtue of one or more carbonyl groups on the binder which react with said amines to form a carbinolamine.

What is claimed is: 
     
       1. A photocrosslinked composition, comprising, as the major portion thereof, a polymeric binder containing a recurring unit bearing one or more carbonyl groups capable of reacting with an amine to form a crosslinked carbinolamine; and   as a minor portion thereof, a thermally stable, reducible cobalt(III) complex containing amine ligands.   
     
     
       2. A composition as defined in claim 1 wherein said binder contains aldehyde groups as said carbonyl groups. 
     
     
       3. A composition as defined in claim 1, wherein said binder contains a recurring unit having the structure: ##STR40## wherein R 1  is hydrogen or carboxyl, R 2  is hydrogen or alkyl containing from 1 to 3 carbon atoms,   R 3  is alkylene, phenylenedialkylene or alkylenephenylene containing from 1 to 5 carbon atoms in the alkylene portions, or phenylene,   and n is 0 or 1.   
     
     
       4. A composition as defined in claim 1, wherein said binder contains a recurring unit having the structure: ##STR41## wherein R 2  is hydrogen or alkyl containing from 1 to 3 carbon atoms. 
     
     
       5. A composition as defined in claim 1, wherein said binder contains a recurring unit having the structure: ##STR42## 
     
     
       6. A composition as defined in claim 1, wherein said binder is a condensation polymer. 
     
     
       7. A composition as defined in claim 1, wherein said binder is a polymer containing recurring units with the structure: ##STR43## wherein R 5  is H or alkyl containing from 1 to 6 carbon atoms, R 6  is H or ##STR44##  provided that in at least 10 mole % of the polymer, R 6  is ##STR45##  and R 7  is alkylene containing from 1 to about 8 carbon atoms.   
     
     
       8. A composition as defined in claim 1, and further including a photoactivator capable of reducing said complex in response to activating radiation having a wavelength longer than about 300 nm. 
     
     
       9. A composition as defined in claim 1, and further including a reducing agent precursor capable in the presence of reduction products of said cobalt(III) complex, of reducing cobalt(III) complex to cause amplification of the crosslinking of said binder. 
     
     
       10. A photocrosslinked composition, comprising, as the major portion thereof, a polymeric binder containing at least two recurring units having the structure: ##STR46##  wherein x and y are molar amounts of the recurring units such that the ratio of x:y is from about 2:8 to about 2:1; and   as a minor portion thereof, a thermally stable reducible cobalt(III) complex containing amine ligands.   
     
     
       11. A composition as defined in claim 10 wherein said complex is tris(trimethylenediamine) cobalt(III) trifluoroacetate. 
     
     
       12. A photocrosslinkable composition, comprising, as the major portion thereof, a polymeric binder containing at least two recurring units having the structure: ##STR47##  wherein x and y are molar amounts of the recurring units such that the ratio of x:y is from 2:8 to about 2:1; and   as a minor portion thereof, a thermally stable, reducible cobalt(III) complex containing amine ligands.   
     
     
       13. A composition as defined in claim 12, wherein said complex is tris(trimethylenediamine) cobalt(III) trifluoroacetate. 
     
     
       14. A photocrosslinkable composition, comprising, as the major portion thereof, a polymeric binder containing at least tow recurring units having the structure: ##STR48##  wherein J is --SO 2  NH--R 10  or --NHSO 2  --R 10 , R 10  is alkyl containing from 1 to 5 carbon atoms and x and y are molar amounts of the recurring units such that the ratio of x:y is from about 2:8 to about 2:1; and   as a minor portion thereof, a thermally stable, reducible cobalt(III) complex containing amine ligands.   
     
     
       15. A composition as defined in claim 14, wherein said complex is tris(trimethylenediamine) cobalt(III) trifluoroacetate. 
     
     
       16. A light-sensitive element, comprising a support bearing a photocrosslinkable layer comprising, as the major portion thereof, a polymeric binder containing a recurring unit bearing one or more carbonyl groups capable of reacting with an amine to form a crosslinked carbinolamine;   and as a minor portion thereof, a thermally stable, reducible cobalt(III) complex containing amine ligands.   
     
     
       17. An element as defined in claim 16, wherein said binder contains aldehyde groups as said carbonyl groups. 
     
     
       18. An element as defined in claim 16, wherein said binder contains a recurring unit having the structure; ##STR49## wherein R 1  is hydrogen or carboxyl, R 2  is hydrogen or alkyl containing from 1 to 3 carbon atoms,   R 3  is alkylene, phenylenedialkylene or alkylenephenylene containing from 1 to 5 carbon atoms in the alkylene portions, or phenylene,   and n is 0 or 1.   
     
     
       19. An element as defined in claim 16, wherein said binder contains a recurring unit having the structure: ##STR50## wherein R 2  is hydrogen or alkyl containing from 1 to 3 carbon atoms. 
     
     
       20. An element as defined in claim 16, wherein said binder contains a recurring unit having the structure: ##STR51## 
     
     
       21. An element as defined in claim 17, wherein said layer includes a photoactivator capable of reducing said complex in response to activating radiation having a wavelength longer than about 300 nm. 
     
     
       22. An element as defined in claim 17, wherein said layer includes a reducing agent precursor capable in the presence of reduction products of said cobalt(III) complex, of reducing said cobalt(III) complex to cause amplification of the crosslinking of said binder. 
     
     
       23. A light-sensitive element useful in forming an ink-water discriminating image comprising (a) a hydrophilic support, said support bearing   (b) a photocrosslinkable composition comprising (i) a thermally stable, reducible cobalt(III) complex containing amine ligands;   (ii) an oleophilic polymer containing a recurring unit bearing one or more carbonyl groups capable of reacting with said amine to photocrosslink the polymer; and   (iii) a reducing agent precursor capable of increasing the speed of said photocrosslinking by generating additional reducing agents for said complex in the presence of reduction products of said complex.     
     
     
       24. A method of imaging an element as defined in claim 23, comprising the steps of: (a) exposing to activating radiation said photocrosslinkable composition of said element; and   (b) developing said exposed photocrosslinkable composition to form an image.